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用于氧化还原应用的超原子的设计与研究:第一性原理研究

Design and Investigation of Superatoms for Redox Applications: First-Principles Studies.

作者信息

Sikorska Celina

机构信息

Faculty of Chemistry, University of Gdańsk, Fahrenheit Union of Universities in Gdańsk, Wita Stwosza 63, 80-308 Gdańsk, Poland.

Department of Physics, The University of Auckland, Private Bag 92019, Auckland 1142, New Zealand.

出版信息

Micromachines (Basel). 2023 Dec 29;15(1):78. doi: 10.3390/mi15010078.

Abstract

A superatom is a cluster of atoms that acts like a single atom. Two main groups of superatoms are superalkalis and superhalogens, which mimic the chemistry of alkali and halogen atoms, respectively. The ionization energies of superalkalis are smaller than those of alkalis (<3.89 eV for cesium atom), and the electron affinities of superhalogens are larger than that of halogens (>3.61 eV for chlorine atom). Exploring new superalkali/superhalogen aims to provide reliable data and predictions of the use of such compounds as redox agents in the reduction/oxidation of counterpart systems, as well as the role they can play more generally in materials science. The low ionization energies of superalkalis make them candidates for catalysts for CO conversion into renewable fuels and value-added chemicals. The large electron affinity of superhalogens makes them strong oxidizing agents for bonding and removing toxic molecules from the environment. By using the superatoms as building blocks of cluster-assembled materials, we can achieve the functional features of atom-based materials (like conductivity or catalytic potential) while having more flexibility to achieve higher performance. This feature paper covers the issues of designing such compounds and demonstrates how modifications of the superatoms (superhalogens and superalkalis) allow for the tuning of the electronic structure and might be used to create unique functional materials. The designed superatoms can form stable perovskites for solar cells, electrolytes for Li-ion batteries of electric vehicles, superatomic solids, and semiconducting materials. The designed superatoms and their redox potential evaluation could help experimentalists create new materials for use in fields such as energy storage and climate change.

摘要

超原子是一类原子簇,其行为类似于单个原子。超原子主要分为超碱和超卤素两类,它们分别模拟碱金属原子和卤素原子的化学性质。超碱的电离能低于碱金属(铯原子的电离能<3.89 eV),超卤素的电子亲和能高于卤素(氯原子的电子亲和能>3.61 eV)。探索新型超碱/超卤素旨在提供可靠的数据,并预测此类化合物在对应体系的还原/氧化过程中作为氧化还原试剂的用途,以及它们在材料科学中更广泛发挥的作用。超碱的低电离能使其成为将CO转化为可再生燃料和高附加值化学品的催化剂候选物。超卤素的大电子亲和能使其成为用于键合和从环境中去除有毒分子的强氧化剂。通过将超原子用作簇组装材料的构建块,我们可以实现基于原子的材料的功能特性(如导电性或催化潜力),同时在实现更高性能方面具有更大的灵活性。这篇专题论文涵盖了设计此类化合物的问题,并展示了对超原子(超卤素和超碱)的修饰如何实现电子结构的调控,以及如何用于创造独特的功能材料。所设计的超原子可形成用于太阳能电池的稳定钙钛矿、电动汽车锂离子电池的电解质、超原子固体和半导体材料。所设计的超原子及其氧化还原电位评估有助于实验人员创造用于储能和气候变化等领域的新材料。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ece9/10820084/3a5fedf98a03/micromachines-15-00078-g001.jpg

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